JP2015000399A - Noble metal catalyst - Google Patents
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 41
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Abstract
Description
本発明は、ガスを検知するガス電極として被検知ガスを電気化学反応させる作用電極、前記作用電極に対する対極、前記作用電極の電位を制御する参照電極を、電解液を収容した電解槽の電解液収容部に臨んで備えた定電位電解式ガスセンサにおける前記各電極の貴金属触媒として使用される貴金属触媒に関する。 The present invention provides a working electrode for electrochemically reacting a gas to be detected as a gas electrode for detecting a gas, a counter electrode for the working electrode, and a reference electrode for controlling the potential of the working electrode. The present invention relates to a noble metal catalyst used as a noble metal catalyst of each electrode in a constant potential electrolytic gas sensor provided facing a housing portion.
従来の定電位電解式ガスセンサは、電極を電解液が密に収容される電解槽の電解液収容部内に臨んで設けて構成してあり、例えば電極としては、ガスを検知するガス電極として被検知ガスを電気化学反応させる作用電極、当該作用電極に対する対極、作用電極の電位を制御する参照電極の3電極を設けてあり、また、これらが接触自在な電解液を収容した電解槽と、各電極の電位を設定するポテンシオスタット回路等を接続してある。前記3電極の材料としては撥水性を有するガス透過性の多孔質PTFE膜に白金や金、パラジウム等の貴金属触媒等を塗布したものが、電解液としては、硫酸やリン酸等の酸性水溶液等が用いられていた。 A conventional constant potential electrolytic gas sensor is configured such that an electrode is provided facing an electrolytic solution storage part of an electrolytic cell in which an electrolytic solution is densely stored. For example, an electrode is detected as a gas electrode that detects gas. There are provided three electrodes, a working electrode for electrochemically reacting gas, a counter electrode for the working electrode, and a reference electrode for controlling the potential of the working electrode. A potentiostat circuit for setting the potential is connected. As the material of the three electrodes, a gas-permeable porous PTFE film having water repellency is coated with a noble metal catalyst such as platinum, gold, palladium, etc. As an electrolyte, an acidic aqueous solution such as sulfuric acid or phosphoric acid is used. Was used.
また、定電位電解式ガスセンサは、周囲の環境変化に対して作用電極の電位を制御して一定に維持することによって、作用電極と対極との間に周囲の環境変化に相当する電流を生じさせる。そして、作用電極の電位が変化せず、またガス種によって酸化還元電位が異なることを利用することにより、ポテンシオスタット回路の設定電位によってはガスの選択的な検知が可能になる。また、ガス電極に用いる触媒を変えることで、目的とするガスに対して高い選択性を持たすことができる。 In addition, the constant potential electrolytic gas sensor generates a current corresponding to a change in the surrounding environment between the working electrode and the counter electrode by controlling the potential of the working electrode to be constant with respect to a change in the surrounding environment. . Further, by utilizing the fact that the potential of the working electrode does not change and the oxidation-reduction potential varies depending on the gas type, the gas can be selectively detected depending on the set potential of the potentiostat circuit. Further, by changing the catalyst used for the gas electrode, it is possible to have high selectivity for the target gas.
電極に塗布する貴金属触媒としては、例えば粒径が数十nmのカーボンに、数百nm程度の金微粒子を付着させたものを使用することがあった。このようにカーボンに金微粒子を付着させるには、例えば浸漬担持法を使用することがある。当該浸漬担持法で貴金属粒子を担体に付着させる場合、当該担体を金属塩の水溶液中に浸して、金属成分を担体表面に吸着させ、乾燥・焼成・還元を行う。当該浸漬担持法で金付着カーボンを作製した後、多孔質PTFE膜に塗布して電極を作製していた。 As a noble metal catalyst applied to an electrode, for example, a carbon particle having a particle size of several tens of nanometers and gold fine particles of about several hundred nanometers attached may be used. In order to attach gold fine particles to carbon in this way, for example, an immersion support method may be used. When the noble metal particles are attached to the support by the immersion support method, the support is immersed in an aqueous solution of a metal salt, the metal component is adsorbed on the support surface, and drying, firing, and reduction are performed. After producing gold-attached carbon by the immersion support method, an electrode was produced by applying it to a porous PTFE membrane.
尚、本発明における従来技術となる上述した定電位電解式ガスセンサは、一般的な技術であるため、特許文献等の従来技術文献は示さない。 Note that the above-described constant potential electrolytic gas sensor, which is a conventional technique in the present invention, is a general technique, and therefore does not show any prior art documents such as patent documents.
上述の手法によって作製された金付着カーボンは、金微粒子の粒径が担体であるカーボンの粒径より大きく、水溶液中で凝集し易い傾向にあるため、金微粒子を均一に分散させるのが困難であった。このように金微粒子が不均一な状態で作製された金付着カーボンを貴金属触媒として使用すると、ガス検知性能がバラつくなどの影響を与えることがあった。 The gold-adhered carbon produced by the above-mentioned method has a particle size of gold fine particles larger than that of carbon as a carrier and tends to aggregate in an aqueous solution, so that it is difficult to uniformly disperse the gold fine particles. there were. When the gold-adhered carbon produced in such a state that the gold fine particles are not uniform is used as a noble metal catalyst, there are cases where the gas detection performance varies.
従って、本発明の目的は、定電位電解式ガスセンサにおける前記各電極の貴金属触媒として使用するに際し、ガス検知性能にバラつきが発生しにくい貴金属触媒を提供することにある。 Accordingly, an object of the present invention is to provide a noble metal catalyst that hardly causes variations in gas detection performance when used as a noble metal catalyst for each electrode in a potentiostatic gas sensor.
上記目的を達成するための本発明に係る貴金属触媒の第一特徴構成は、担体としてのカーボン粉末に、前記カーボン粉末の平均粒径以下の平均粒径を有する金ナノ粒子を担持させた点にある。 The first characteristic configuration of the noble metal catalyst according to the present invention for achieving the above object is that gold nanoparticles having an average particle size equal to or smaller than the average particle size of the carbon powder are supported on the carbon powder as a support. is there.
本構成の貴金属触媒は、カーボン粉末の平均粒径以下の平均粒径を有する金ナノ粒子を担持させることで、金ナノ粒子を分散させた状態で担体であるカーボンに担持させることができるため、金ナノ粒子の分散の程度を概ね均一な状態とすることができる。そのため、このような金担持カーボンを、例えばガスセンサにおける貴金属触媒として使用すれば、ガス検知性能にバラつきが生じるのを未然に防止することができる。 Since the noble metal catalyst of this configuration supports gold nanoparticles having an average particle size equal to or less than the average particle size of the carbon powder, the gold nanoparticles can be supported on the carrier carbon in a dispersed state. The degree of dispersion of the gold nanoparticles can be made substantially uniform. Therefore, if such a gold-supporting carbon is used as a noble metal catalyst in a gas sensor, for example, it is possible to prevent the gas detection performance from varying.
尚、本明細書では、カーボン粉末の平均粒径以下の平均粒径を有する金ナノ粒子を付着させることを「担持」と称し、カーボン粉末の平均粒径より大きな平均粒径を有する金ナノ粒子が付着した従来の金付着カーボンと区別している。 In the present specification, attaching gold nanoparticles having an average particle size equal to or less than the average particle size of carbon powder is referred to as “supporting”, and gold nanoparticles having an average particle size larger than the average particle size of carbon powder. It is distinguished from the conventional gold-attached carbon to which is attached.
本発明に係る貴金属触媒の第二特徴構成は、前記金ナノ粒子は、5〜50nmの粒子が5〜50重量%で担持される点にある。 The second characteristic configuration of the noble metal catalyst according to the present invention is that the gold nanoparticles are supported at 5 to 50% by weight of 5 to 50 nm particles.
本構成であれば、金ナノ粒子をカーボン粉末に良好に分散させた状態でカーボン粉末に担持させることができる。 With this configuration, the gold nanoparticles can be supported on the carbon powder in a state of being well dispersed in the carbon powder.
また、後述の実施例では、各電極で使用する金担持カーボンにおいて、金ナノ粒子の含有量を5〜50重量%まで種々変更して、それぞれにおいて定電位電解式ガスセンサを作製した。この結果、当該金ナノ粒子の添加量が5重量%以上であれば安定したガス感度が得られ、金担持カーボンの製造コストを鑑みると、金担持カーボンにおける金ナノ粒子の添加量が50重量%までに抑制するのがよいものと認められた。 Moreover, in the below-mentioned Example, in the gold | metal | money carrying | support carbon used with each electrode, content of gold nanoparticles was variously changed to 5 to 50 weight%, and the constant potential electrolytic gas sensor was produced in each. As a result, stable gas sensitivity can be obtained if the added amount of the gold nanoparticles is 5% by weight or more, and the added amount of the gold nanoparticles in the gold-supported carbon is 50% by weight in view of the production cost of the gold-supported carbon. It was recognized that it should be suppressed by
本発明に係る貴金属触媒の第三特徴構成は、前記カーボン粉末の粒径を5〜300nmの範囲にあるものとした点にある。 The third characteristic configuration of the noble metal catalyst according to the present invention is that the particle size of the carbon powder is in the range of 5 to 300 nm.
本構成では、カーボン粉末の粒径を5〜300nmの範囲にある任意の粒径に設定し、金ナノ粒子の粒径を、当該任意の粒径以下に設定することができる。具体的には、例えばカーボンブラックの粒度を、このような粒径の範囲を有するように調整して使用することができる。 In this configuration, the particle size of the carbon powder can be set to an arbitrary particle size in the range of 5 to 300 nm, and the particle size of the gold nanoparticle can be set to be equal to or less than the arbitrary particle size. Specifically, for example, the particle size of carbon black can be adjusted to have such a particle size range.
本発明に係る貴金属触媒の第四特徴構成は、前記金ナノ粒子を担持させた前記カーボン粉末を250〜450℃で焼成して作製した点にある。 The fourth characteristic configuration of the noble metal catalyst according to the present invention is that the carbon powder supporting the gold nanoparticles is produced by firing at 250 to 450 ° C.
浸漬担持法における焼成の温度は600℃程度とすることがあるが、担体をカーボンとする場合に焼成の温度がこのように高温であると、担体であるカーボンが燃焼してしまう虞があった。
一方、本構成による貴金属触媒は、作製の過程で焼成の温度を250〜450℃に抑制することができるため、担体であるカーボンが燃焼する虞はない。
The calcination temperature in the immersion support method may be about 600 ° C. However, when the carrier is carbon, if the calcination temperature is such a high temperature, the carbon as the carrier may burn. .
On the other hand, the precious metal catalyst according to the present configuration can suppress the firing temperature to 250 to 450 ° C. during the production process, and therefore there is no possibility that carbon as a carrier burns.
本発明に係る貴金属触媒の第五特徴構成は、前記貴金属触媒が、ガスを検知するガス電極として被検知ガスを化学反応させる作用電極、前記作用電極に対する対極、前記作用電極の電位を制御する参照電極を、電解液を収容した電解槽の電解液収容部に臨んで備えた定電位電解式ガスセンサにおける前記各電極の貴金属触媒として使用される点にある。 According to a fifth feature of the noble metal catalyst of the present invention, the noble metal catalyst controls a working electrode that chemically reacts with a gas to be detected as a gas electrode for detecting gas, a counter electrode for the working electrode, and a potential for controlling the potential of the working electrode. The electrode is used as a noble metal catalyst of each electrode in a constant potential electrolysis gas sensor equipped with an electrode facing an electrolyte solution storage part of an electrolytic cell containing an electrolyte solution.
本構成の貴金属触媒は、金ナノ粒子を分散させた状態で担体であるカーボンに担持させることができるため、金ナノ粒子の分散の程度を概ね均一な状態とすることができる。そのため、このような金担持カーボンを貴金属触媒として使用すれば、定電位電解式ガスセンサにおいて、ガス検知性能にバラつきが生じるのを未然に防止することができる。 Since the noble metal catalyst of this configuration can be supported on carbon as a carrier in a state where gold nanoparticles are dispersed, the degree of dispersion of the gold nanoparticles can be made substantially uniform. Therefore, if such a gold-supported carbon is used as a noble metal catalyst, it is possible to prevent the gas detection performance from varying in the constant potential electrolytic gas sensor.
以下、本発明の実施形態を図面に基づいて説明する。
本発明の貴金属触媒は、定電位電解式ガスセンサにおける各電極の貴金属触媒として使用される。
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
The noble metal catalyst of the present invention is used as a noble metal catalyst for each electrode in a potentiostatic gas sensor.
当該貴金属触媒は、担体としてのカーボン粉末に、前記カーボン粉末の平均粒径以下の平均粒径を有する金ナノ粒子を担持させている。 In the noble metal catalyst, gold nanoparticles having an average particle size equal to or less than the average particle size of the carbon powder are supported on carbon powder as a carrier.
図1に示すように、定電位電解式ガスセンサXは、ガスを検知するガス電極として被検知ガスを電気化学反応させる作用電極11、当該作用電極11に対する対極12、作用電極の電位を制御する参照電極13を、電解液20を収容した電解槽30の電解液収容部31に臨んで備えている。 As shown in FIG. 1, the constant potential electrolysis gas sensor X is a gas electrode for detecting a gas. A working electrode 11 for electrochemically reacting a gas to be detected, a counter electrode 12 for the working electrode 11, and a reference for controlling the potential of the working electrode. The electrode 13 is provided so as to face the electrolytic solution storage part 31 of the electrolytic bath 30 in which the electrolytic solution 20 is stored.
作用電極11、対極12及び参照電極13は、撥水性を有する多孔質のガス透過膜14の表面に、公知の電極材料より作製したペーストを塗布・焼成して形成してある。作用電極11と、対極12及び参照電極13とは、対向して配置してある。 The working electrode 11, the counter electrode 12, and the reference electrode 13 are formed by applying and baking a paste made of a known electrode material on the surface of a porous gas-permeable film 14 having water repellency. The working electrode 11, the counter electrode 12 and the reference electrode 13 are disposed to face each other.
電解槽30は側方に開口する開口部32を形成してガス導通部33を形成している。ガス透過膜14は二枚設けられ、一方のガス透過膜14には作用電極11が配設され、他方のガス透過膜14には対極12及び参照電極13が配設される。作用電極11の側に配設されたガス透過膜14は、開口部32に臨むように電解槽30に取り付けられる。被検知ガスはガス導通部33より導入され、作用電極11上で反応する。 The electrolytic cell 30 forms a gas conduction part 33 by forming an opening part 32 that opens to the side. Two gas permeable membranes 14 are provided. One gas permeable membrane 14 is provided with a working electrode 11, and the other gas permeable membrane 14 is provided with a counter electrode 12 and a reference electrode 13. The gas permeable membrane 14 disposed on the working electrode 11 side is attached to the electrolytic cell 30 so as to face the opening 32. The gas to be detected is introduced from the gas conduction part 33 and reacts on the working electrode 11.
それぞれのガス透過膜14とOリング15とは蓋部材16によって固定される。電解槽30の底面には、電解液20の注入等のメンテナンスを行う電解液注入口34が形成されている。 Each gas permeable membrane 14 and the O-ring 15 are fixed by a lid member 16. An electrolytic solution inlet 34 for performing maintenance such as injection of the electrolytic solution 20 is formed on the bottom surface of the electrolytic bath 30.
このような定電位電解式ガスセンサXは、被検知ガスの反応によって作用電極11上で生じた電子に基づく電流を検知自在な電流測定部と、作用電極11の電位制御自在な電位制御部とを備えたガス検知回路(図外)に接続して、ガス検知装置として用いられる。本発明の定電位電解式ガスセンサXは、例えばシラン、ホスフィン、ゲルマン、アルシン、ジボランなどの水素化物ガスの検知に用いられる。 Such a constant potential electrolytic gas sensor X includes a current measuring unit capable of detecting a current based on electrons generated on the working electrode 11 by a reaction of the gas to be detected, and a potential control unit capable of controlling the potential of the working electrode 11. It is used as a gas detection device by connecting to a gas detection circuit (not shown). The constant potential electrolytic gas sensor X of the present invention is used for detection of hydride gas such as silane, phosphine, germane, arsine, diborane.
図2に示したように、定電位電解式ガスセンサXにおける各電極10は貴金属触媒を備えており、当該貴金属触媒は、溶媒にカーボン粉末および界面活性剤を添加して撹拌するカーボン粉末添加工程Aと、金ナノ粒子を分散させたコロイド溶液を添加する金ナノ粒子添加工程Bと、溶媒の沸点以下に維持した状態で乾燥させる乾燥工程Cと、乾燥して得られた粉末を250〜450℃で焼成を行う焼成工程Dと、を行って作製される。 As shown in FIG. 2, each electrode 10 in the potentiostatic gas sensor X includes a noble metal catalyst, and the noble metal catalyst is added with a carbon powder and a surfactant in a solvent and agitated. And a gold nanoparticle addition step B for adding a colloidal solution in which gold nanoparticles are dispersed, a drying step C for drying in a state maintained below the boiling point of the solvent, and a powder obtained by drying at 250 to 450 ° C. And firing step D in which firing is performed.
カーボン粉末添加工程Aでは、カーボン粉末を所定量秤量し、界面活性剤、溶媒である水を加え十分攪拌させる。
カーボン粉末は、公知のカーボン粉末、例えばカーボンブラック(粒径5〜300nm程度:平均粒径20nm)を使用することができ、特にアセチレンガスを熱分解して得るアセチレンブラックを使用するのがよいが、これに限定されるものではない。
In the carbon powder addition step A, a predetermined amount of carbon powder is weighed, and a surfactant and water as a solvent are added and sufficiently stirred.
As the carbon powder, a known carbon powder, for example, carbon black (particle size of about 5 to 300 nm: average particle size of 20 nm) can be used, and in particular, acetylene black obtained by thermally decomposing acetylene gas is preferably used. However, the present invention is not limited to this.
界面活性剤は、アニオン系、カチオン系、ノニオン系、ベタイン系界面活性剤のいずれも使用できる。 As the surfactant, any of anionic, cationic, nonionic, and betaine surfactants can be used.
金ナノ粒子添加工程Bでは、カーボン粉末添加工程Aで得られた溶液に金ナノ粒子を分散させたコロイド溶液を添加する。
金ナノ粒子(平均粒径10nm)を分散させたコロイド溶液は、上述した粒度を有する金ナノ粒子が溶液中に分散している状態となっている。当該コロイド溶液には、必要に応じて保護剤などの添加剤を添加してもよい。
金コロイド溶液は、例えばテトラクロロ金酸(III)などの塩化金酸溶液に還元剤としてクエン酸塩溶液を加えて加熱することにより、金属イオンを還元してコロイドとする溶液内還元反応を利用して作製することができるが、このような手法に限定されるものではない。当該方法においては、塩化金酸に対する還元剤の添加量を増減することにより、金コロイド粒子の大きさを変化させることができる。金ナノ粒子は、約5〜50nm程度の粒径を有する粒子であればよいが、この範囲に限定されるものではない。この場合、5〜50nmの粒子の割合が90重量%以上となるような粒度分布とするのがよい。
In the gold nanoparticle addition step B, a colloidal solution in which gold nanoparticles are dispersed in the solution obtained in the carbon powder addition step A is added.
The colloidal solution in which gold nanoparticles (average particle size 10 nm) are dispersed is in a state in which the gold nanoparticles having the above-described particle size are dispersed in the solution. You may add additives, such as a protective agent, to the said colloid solution as needed.
The colloidal gold solution uses an in-solution reduction reaction in which metal ions are reduced to a colloid by adding a citrate solution as a reducing agent to a chloroauric acid solution such as tetrachloroauric acid (III) and heating. However, it is not limited to such a method. In this method, the size of colloidal gold particles can be changed by increasing or decreasing the amount of reducing agent added to chloroauric acid. The gold nanoparticles may be particles having a particle size of about 5 to 50 nm, but are not limited to this range. In this case, the particle size distribution is preferably such that the ratio of 5 to 50 nm particles is 90% by weight or more.
乾燥工程Cでは、金ナノ粒子添加工程Bで得られた溶液を、溶媒(水)の沸点以下に維持した状態で乾燥させる。溶媒の沸点以下として設定する温度は、特に限定されるものではないが、溶媒が水の場合、80〜100℃程度とするのがよい。乾燥の手法は、例えば減圧乾燥、真空乾燥、吸引乾燥、熱風乾燥など、公知の手法を適用することができる。これら乾燥の手法における乾燥条件は、公知の条件を適用すればよい。 In the drying step C, the solution obtained in the gold nanoparticle addition step B is dried in a state where the solution is kept below the boiling point of the solvent (water). Although the temperature set as below the boiling point of a solvent is not specifically limited, When a solvent is water, it is good to set it as about 80-100 degreeC. As a drying method, a known method such as reduced-pressure drying, vacuum drying, suction drying, or hot air drying can be applied. Known conditions may be applied as drying conditions in these drying methods.
焼成工程Dでは、乾燥して得られた粉末を250〜450℃で焼成を行う。
本実施形態における焼成温度は、空気雰囲気、大気圧下でカーボンの酸化が進まない温度で、使用した界面活性剤等の有機物が蒸発する温度(250〜450℃)としてある。
焼成時間は、界面活性剤、コロイドの保護剤等が蒸発、昇華、熱分解により完全になくなるまでの時間を適宜設定すればよい。そのため、焼成させる粉体の量で、その都度焼成時間の短縮・延長が可能である。しかし、金ナノ粒子の粒成長、焼結による活性の低下などを考慮して、例えば当該焼成時間の上限を3時間程度までと設定してもよい。また、焼成時間を設定せず、所定の温度に達すれば焼成工程Dを終了するように設定してもよい。
In the firing step D, the powder obtained by drying is fired at 250 to 450 ° C.
The firing temperature in the present embodiment is a temperature (250 to 450 ° C.) at which the organic matter such as the used surfactant evaporates at a temperature at which carbon oxidation does not proceed under an air atmosphere and atmospheric pressure.
The firing time may be set as appropriate until the surfactant, colloid protective agent, and the like are completely eliminated by evaporation, sublimation, and thermal decomposition. Therefore, the firing time can be shortened or extended each time depending on the amount of powder to be fired. However, in consideration of grain growth of gold nanoparticles, a decrease in activity due to sintering, etc., the upper limit of the firing time may be set to about 3 hours, for example. Moreover, you may set so that the baking process D may be complete | finished if it reaches predetermined temperature, without setting baking time.
上記手法によって、金ナノ粒子を分散させた状態で担持する金担持カーボンを作製することができる。即ち、定電位電解式ガスセンサXは、金ナノ粒子を分散させた状態で担持する金担持カーボンを貴金属触媒として使用することができる。当該金担持カーボンは、作製の過程でコロイド溶液を使用しているため、金ナノ粒子を分散させた状態で担体であるカーボンに担持させることができるため、金ナノ粒子の分散の程度を概ね均一な状態とすることができる。そのため、このような金担持カーボンを貴金属触媒として使用すれば、定電位電解式ガスセンサXにおいて、ガス検知性能にバラつきが生じるのを未然に防止することができる。 By the above method, gold-carrying carbon that carries gold nanoparticles in a dispersed state can be produced. That is, the potentiostatic gas sensor X can use, as a noble metal catalyst, gold-supported carbon that is supported in a state where gold nanoparticles are dispersed. Since the gold-supporting carbon uses a colloidal solution in the production process, it can be supported on carbon as a carrier in a state in which the gold nanoparticles are dispersed, so the degree of dispersion of the gold nanoparticles is almost uniform. It can be in a state. Therefore, if such gold-supported carbon is used as a noble metal catalyst, it is possible to prevent the gas detection performance from varying in the constant potential electrolytic gas sensor X.
また、本構成による金担持カーボンは、作製の過程で焼成の温度を250〜450℃に抑制することができるため、担体であるカーボンが燃焼する虞はない。 In addition, since the gold-supporting carbon according to this configuration can suppress the firing temperature to 250 to 450 ° C. during the production process, there is no possibility that the carbon serving as the carrier will burn.
さらに、上記手法で作製した金担持カーボンにおいて、金ナノ粒子は、約5〜50nm程度の粒径で分散させることが可能となる。その結果、従来の手法により作製した金担持カーボンにおける金微粒子の添加量が50重量%より多いのに対して、上記手法で作製した金担持カーボンにおける金ナノ粒子の添加量を5〜50重量%に減じることができる。従って、本発明の定電位電解式ガスセンサXは、貴金属触媒における金ナノ粒子の添加量を減じることができるため、センサの製造コストを削減することができる。 Furthermore, in the gold-supported carbon produced by the above method, the gold nanoparticles can be dispersed with a particle size of about 5 to 50 nm. As a result, the amount of added gold fine particles in the gold-supported carbon prepared by the conventional method is more than 50% by weight, whereas the amount of gold nanoparticles added in the gold-supported carbon prepared by the above method is 5 to 50% by weight. Can be reduced to Therefore, since the controlled potential electrolytic gas sensor X of the present invention can reduce the amount of gold nanoparticles added to the noble metal catalyst, the manufacturing cost of the sensor can be reduced.
〔実施例1〕
定電位電解式ガスセンサXの電極において貴金属触媒として使用する金担持カーボンを以下のようにして作製した。当該金担持カーボンに対する金ナノ粒子の含有量が25重量%になるように、各試薬を調整した。
[Example 1]
A gold-supporting carbon used as a noble metal catalyst in the electrode of the potentiostatic gas sensor X was prepared as follows. Each reagent was adjusted so that the content of the gold nanoparticles with respect to the gold-supported carbon was 25% by weight.
アセチレンブラック粉末3gと、界面活性剤(ドデシルベンゼンスルホン酸ナトリウム)2mLを水600mLに添加して十分撹拌した(カーボン粉末添加工程A)。
この撹拌溶液に、金ナノ粒子を分散させたコロイド水溶液(3重量%)を33.3gを添加した(金ナノ粒子添加工程B)。
その後、攪拌を続けながら80℃に保持し、さらに減圧乾燥(100hpa、80℃)させた(乾燥工程C)。
乾燥後、取り出した試料粉末を大気圧、空気雰囲気下で400℃、1時間の焼成を行い金担持カーボンの粉末を得た(本発明例1)。
3 g of acetylene black powder and 2 mL of a surfactant (sodium dodecylbenzenesulfonate) were added to 600 mL of water and sufficiently stirred (carbon powder addition step A).
To this stirring solution, 33.3 g of a colloidal aqueous solution (3% by weight) in which gold nanoparticles were dispersed was added (gold nanoparticle addition step B).
Then, it kept at 80 degreeC, continuing stirring, and also made it dry under reduced pressure (100 hpa, 80 degreeC) (drying process C).
After drying, the sample powder taken out was baked at 400 ° C. for 1 hour under atmospheric pressure and air atmosphere to obtain gold-supported carbon powder (Invention Example 1).
本発明例1の金ナノ粒子の粒度分布(X線小角散乱法による測定)を図3に示し、金担持カーボンの電子顕微鏡写真を図4に示した。図5には、比較として従来の金担持カーボン(比較例)の電子顕微鏡写真を示した。 The particle size distribution (measured by the X-ray small angle scattering method) of the gold nanoparticles of Example 1 of the present invention is shown in FIG. 3, and an electron micrograph of the gold-supporting carbon is shown in FIG. FIG. 5 shows an electron micrograph of a conventional gold-supporting carbon (comparative example) for comparison.
図3より、当該金ナノ粒子の粉末は5〜50nm程度の粒径を有するものと認められた。また、本発明例1の金担持カーボンでは、金ナノ粒子が分散してカーボンに担持されていると認められた(図4)。一方、比較例の金担持カーボンでは、金微粒子が凝集しているものと認められた(図5)。 From FIG. 3, it was recognized that the powder of the said gold nanoparticle has a particle size of about 5-50 nm. In the gold-supported carbon of Invention Example 1, it was recognized that the gold nanoparticles were dispersed and supported on the carbon (FIG. 4). On the other hand, in the gold-supporting carbon of the comparative example, it was recognized that the gold fine particles were aggregated (FIG. 5).
〔実施例2〕
定電位電解式ガスセンサXの各電極を以下のようにして作製した。各電極で使用する金担持カーボンにおいて、金ナノ粒子の含有量を5〜50重量%まで種々変更して、それぞれにおいて定電位電解式ガスセンサXを作製した。
[Example 2]
Each electrode of the potentiostatic gas sensor X was produced as follows. In the gold-supporting carbon used in each electrode, the content of the gold nanoparticles was variously changed from 5 to 50% by weight, and a potentiostatic gas sensor X was produced in each.
金担持カーボンの粉末0.1g、界面活性剤(ドデシルベンゼンスルホン酸ナトリウム)0.1mL、PTFE(ポリテトラフルオロエチレン:テフロン)ディスパージョン(PTFEの微粒子を含むコロイド溶液、比重1.5)0.35mLをそれぞれ加え、混錬して電極材料ペーストを調製した。得られた電極材料ペーストをPTFEシート上に印刷し、乾燥後、280℃で8時間焼成することで各電極10を得た。得られた各電極10を、それぞれ作用電極11、対極12及び参照電極13とし、電解液20を42重量%の硫酸水溶液とした定電位電解式ガスセンサXを作製した。 0.1 g of gold-supported carbon powder, 0.1 mL of surfactant (sodium dodecylbenzenesulfonate), PTFE (polytetrafluoroethylene: Teflon) dispersion (a colloidal solution containing fine particles of PTFE, specific gravity 1.5). 35 mL of each was added and kneaded to prepare an electrode material paste. The obtained electrode material paste was printed on a PTFE sheet, dried, and baked at 280 ° C. for 8 hours to obtain each electrode 10. Each of the obtained electrodes 10 was used as a working electrode 11, a counter electrode 12, and a reference electrode 13, and a potentiostatic gas sensor X was prepared in which the electrolytic solution 20 was a 42% by weight sulfuric acid aqueous solution.
得られたそれぞれの定電位電解式ガスセンサXにおいて、20℃、50%RH環境下で、ホスフィンガス1ppm,0.5ppmに対するガス感度測定を行った(図6)。同様に、シラン、ホスフィン、ゲルマン、アルシン、ジボランの各ガス1ppmに対してのガス感度測定を行った(図7)。
尚、ガス感度は、対象ガス雰囲気中で、作用電極11からガス検知回路40へ流れる電流値の大きさで定義した。
In each of the obtained potentiostatic gas sensors X, gas sensitivity was measured for phosphine gas 1 ppm and 0.5 ppm in an environment of 20 ° C. and 50% RH (FIG. 6). Similarly, gas sensitivity measurement was performed for 1 ppm of each gas of silane, phosphine, germane, arsine, and diborane (FIG. 7).
The gas sensitivity was defined by the magnitude of the current value flowing from the working electrode 11 to the gas detection circuit 40 in the target gas atmosphere.
この結果、金担持カーボンにおける金ナノ粒子の添加量が5重量%以上、特に20重量%以上である定電位電解式ガスセンサXであればガスに対する反応性が十分高い作用電極であることが認められた。また、金担持カーボンの製造コストを鑑みると、金担持カーボンにおける金ナノ粒子の添加量が50重量%、好ましくは30重量%までに抑制するのがよい。従って、ガス感度および製造コストを考慮すれば、金担持カーボンにおける金ナノ粒子の添加量は5〜50重量%とするのがよい。 As a result, the potentiostatic gas sensor X in which the amount of added gold nanoparticles in the gold-supported carbon is 5% by weight or more, particularly 20% by weight or more is recognized as a working electrode having a sufficiently high reactivity to gas. It was. In view of the production cost of the gold-supported carbon, the amount of gold nanoparticles added to the gold-supported carbon should be suppressed to 50% by weight, preferably 30% by weight. Therefore, in consideration of gas sensitivity and production cost, the amount of gold nanoparticles added to the gold-supported carbon is preferably 5 to 50% by weight.
本発明は、ガスを検知するガス電極として被検知ガスを電気化学反応させる作用電極、前記作用電極に対する対極、前記作用電極の電位を制御する参照電極を、電解液を収容した電解槽の電解液収容部に臨んで備えた定電位電解式ガスセンサにおける前記各電極の貴金属触媒として使用される貴金属触媒に利用できる。 The present invention provides a working electrode for electrochemically reacting a gas to be detected as a gas electrode for detecting a gas, a counter electrode for the working electrode, and a reference electrode for controlling the potential of the working electrode. The present invention can be used for a noble metal catalyst used as a noble metal catalyst for each of the electrodes in a constant potential electrolytic gas sensor provided facing a housing portion.
X 定電位電解式ガスセンサ
11 作用電極
12 対極
13 参照電極
20 電解液
30 電解槽
31 電解液収容部
X constant potential electrolytic gas sensor 11 working electrode 12 counter electrode 13 reference electrode 20 electrolytic solution 30 electrolytic bath 31 electrolytic solution storage
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WO2017022662A1 (en) * | 2015-08-01 | 2017-02-09 | 立山マシン株式会社 | Powder composite in which metallic nanoparticles are supported, and method for producing said powder composite |
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